Chlorination process



Dec. 8, 1959 'r. E. STRETTON ETAL I 2,916,423

MELTING POINT C OF WAX l\ N l TTTTTTTTTTTTTT 0N LLLLLLLLLLLLL ER invention relates to a process of 'chlorinating waxes and the chlorinated products derived therefrom. MQreP I i hrly, the invention pertains ,to a chlorination, process wherein mixtures of soft wax and oil are e di at awn c Ychlorinated toobtain stable compositions having high melting points.

Alarge numberof. processes for the chlorination of pairin {waxes have been disclosed, in .the art. When pifodllcing a high melting point product, these processes have generallyjcomprised chlorinating a refined paraffin with gaseous chlorine in the presence of a volatile Solvent under well established temperature and pressure conditions. Actinic light and various chemical catalysts have often been employed to promote the chlorination reaction. The conventional chlorination methods, howeve'ig ha v e not been able to effectively utilize a soft .wax td'pr'oduce a highly chlorinated product having a high melting, point, stability and a white or substantially color.- appearance. has been found, for example, that when high molecular'weight hydrocarbons such as waxes are .chlo r'inated'severe stability problems and undesirable eolors are encountered at elevated temperatures. One objectof the invention is the preparation of chlorinated Eva x compositions having the properties outlined above. e ifobj ect of this iriven'tion'is' touprepar'e such chloe rmated wax'compositions in the absence of solvents which have tobe subsequently separated from the reaction products." Qther objects of the invention will become apparent from the following description. In accordance with the present invention, it has now been, found that a chlorinated waxproduct having a high chlorine content as well as the desired melting point, stability, and color propertiesmay, be preparedby chlorinating 'warn, feed mixture comprising a major proportion of a soft'parafhn wax and a minor proportion of a hydrocarbon oil. The chlorinated waxes prepared by thepi ocess of the. invention may be employed, in many ofth'e conventional chlorinated wax applications. These ehlt iri ated waxes may, for example, be used for imparting water and'fire resistance to v'arious, materials. Aparticularly, outstanding use ofthe chlorinated waxes ofthe invention is in. the preparation of mastic tiles, having exeue t oil resistance, grease resistance and hardness cha r'acteristics.v More specifically, it has. been found that a ehlorinated wax prepared according to the process of this inyention and having a chlorine content within the, range of about.5 6.to 60%, preferably about 57 to 59% and ,a,melting-,po intof about 40,t'o .44, C.,.preferably about "41to 43.? C., is. especially useful inithe, prepara;

tionof mastic floor'and, wall tiles.

LI" enerahthe wax feed mixtures useful for the purposes of the inventioncomp rise about 55 to 80%, prefer ably about;60 to wt. percent of a soft paraffin wax and ah'ontj'Z'OSto 45%, preferably about 25 to 40 wt. percent offa normally; liquid paraffinic hydrocarbon oil. The parafiin waxispreferably a softor slop wax having an AST ,r'neltin gpoint of about 37 to 47 C., an API grfav y' of about42 to46, an ASTM penetration of at least 3.17 and a molecular weight of about 280 to 400. Th ydrocarbon oil maycomprise straight or branched ch aliphatic hydrocarbonsor mixtures thereof having a moleeular, weight ,within the range-of ab0 l'LZ30. to 400, a viscosity index'of about to 105, a viscosity of 2,916,428 Patented Dec.

, y 2 about 1055813 .at F.,.and 40 SSU at 210 F.,..and .an ,APl fgravity ,of about 30 .to 34. Preferably, the hydrocar'bonfloil employed will have an average'mo'lecula'r Weight attleast equal to the molecular weight of the wax. Both the wax ,and hydrocarbon oil may be derived from various ,paraflinic ,or mixed 'base petroleum crudes by conventional refining methods used .in the production of refined waxes and lubricating oil base stocks.

In accordance with another aspect of the invention, it has .been'found thata minorproportion of a solvent may be advantageously employed in conjunction with the fore- .going wax and hydrocarbon oil materials to makeup' the wax feed frrihrture Though the theory is not entirely understood, the use of the solvent appears to minimize the foaming ,difiiculties which are sometimes encountered in the chlorination of parafiin waxes. The solvent employed Iiiust be of such a nature that its separation from the other chlorination products is not necessary. The solvent will generally comprise a mixture of highly branchedchainsaturated hydrocarbons having eleven or more .carbon atoms, preferably about C to C with a boiling point within the range of about 176 to 260 C., andan average molecular weight of about 160 to 190. A particularly effective solvent is the heavy ends obtained from the reaction of butylene with isobutane as is done in the preparation of alkylate to be used for gasoline, blending. This solvent has the following specification:

Boiling point Q. .190-240 C., 50% 204 C. Aniline. point 84-92. Flash. point F. Specific gravity 0.7682. Average molecular wt. 180. Constituents- Olefins 2; 5.7%. Saturates 83.0%. Naphthenes 11.3%. 1

When the solvent is employed the feed mixture will comprise about 50 to 75 preferably about '57 to 65%, by weight of the soft wax; about 20 to 35%, preferably about 28 to 31% ,lby weight of the hydrocarbon .oil; and about 2 to 25%, preferably about 5 to 15%, by weight ofthe solvent.

The soft wax-oil feed mixture of the invention with or without the use of :the aforesaid solvent may-be chlorinated by conventional means. It is preferred, howeyer, that the chlorination be carried out by passing gaseous chlorine through the wax mixture at a reactiontempera: ture of about 212 to--230 F. and under superatmo's- Iphjeric pressure, ,e;g about 10 to 100 p.s.i.g. in the pre'sence or absence of actinic light or chemical catalysts. Chlorination maybe continued until the desiredchlorine contenthas been achieved. Time periods within the range of about 10 to 40 hours are usually sufiicicntflfor the purposes of the present invention. Either batehor continuous operations may be employed. Itis, toner-3 ample, within the scope of this invention to utilize aseries of two to four or more chlorination reactorsiwith a continuous countercurrent flow of, the gaseous chlorine; and Wax feed mixture. The series of chlorination'fre actor's may also be operated batch=wise with thefresh: chlorine gas beingfirst passed into the end'. reactor.

then to eachof the preceding reactors.

clude various inorganic and organic compounds knownto the art. Illustrativestabiilzers include: glycol'ssuch as Usually, the chlorinatedwax prepared in accordance with this invention will be blown with air 'or nitrogen to removefree chlorine and hydrogen chloride. It will ethylene glycol and propylene glycol, polymers of epoxyultraviolet lamps, mercury vapor arc lamps, fluorescent lamps, ordinary light bulbs, and the like. M

The invention will be further understood by reference to the following example: f

EXAMPLE A number of wax feed mixtures, as listed below in the table, were chlorinated as follows: i

The wax feed mixture was subjected to chlorination in a four step batch operation. The fresh feed wax mix- .ture was fed to the first chlorination reactor, andthen successively to each of the three remaining chlorination 'reactors. Fresh gaseous chlorine was fed directlytohthe fourth reactor in the series and then successively to each of the preceding reactors. Consequently, the fresh feed wax was contacted with a gaseous mixture comprising chlorine and hydrogen chloride. The degree of chlorin ation was increased asthe wax feed mixture was passed from the first through the fourth chlorinaton reactor. A temperature of about 105 C. and a pressure not exceeding 50 p.s.i.g. was maintained in each of the chlorination reactors. The time period required to chlorinate the feed material varied from about 10 to 15 hours. The chlorinated waxrecovered from the fourth chlorination vessel was air blown at a temperature of about 105 C. to remove residual chlorine andhydrogen chloride. i

The composition of the wax feed mixtures and the characteristics of the finished chlorinated wax products is tabulated below: i

Table Wax Feed Mixture Chlorinated Wax Wt. per- Run cent Wt. Per- Wt. Per- Solvent 8 Percent M.P., cent cent 01 O. Wax 1 Oil I 60. 0 59 49 60. O 58 45 60. 0 57 41 60. 0 56. 5 39 60. 0 56 37 65. 0 59 47 65. 0 58 43. 3 65. 0 57 39. 5 65. 0 56 35. 8 63. 7 60 49. 3 63. 7 59 45. 5 63. 7 58 42 63. 7 31. 57. 5 40 63. 7 57 38. 3 72. 3 59 44. 4 72. 3 58. 5 42. 5 72. 3 5s 41. 2 72. 3 57. 5 38. 8 72. 3 57 i 37 57. 0 60 44. 2 57. 0 59. 5 42. 5 57. 0 59 40. 7 57. 0 58. 5 38; 9 57. 0 57 33. 5 87. 0 62 47. 8 87. 0 61 40. 5 87. 0 3. 60. 5 38. 1 87. 0 13. 0 60 35. 7 82. 6 12. 4 5. 0 62 49. 7 82. 6 12. 4 5. 0 61 40 82. 6 l2. 4 5. 0. 60. 5 36.3 82. 6 l2. 4 5. 0 60 35. 2 74. 0 11. 0 15. 0 62 43. 1 74. 0 11. 0 15. 0 61 38. 5 74. 0 11.0 15.0 60. 5 36. 3 74. 0 11. 0 15. 0 62 34 65. 2 9. 8 .25. 0 61 40 65. 2 9. 8 25. 0 60. 5 34. 9 65. 2 9. 8 25. 0 60. 5 32 I The hydrocarbon oil employed had the following sptgcilt lcationz A flash point of 380 F., 95 V.I., and a viscosity of 65 SUS 130 i The solvent is one described in column 2 of the specification,

In the accompanying graph, percentage chlorine is plotted against melting point data obtained frornthe chlorinated wax properties tabulated above. The relationship between the plotted curves and the runs is as follows: f Y

Runs

6 to 9 10m 14 20 to 24 25 r0128 29 to 32 33 to 36 37 to 39 The rectangular area. defined by dotted line X sets the bounds .within which the properties of the desired chlo rinatedwax composition fall, i.e. a melting point of about 40 to 44 C. and a chlorinecontent of about 56 to 60%. Dotted line Y, on the other hand, sets the bounds of the preferred properties, Le. a melting point of about 41 to 43 C., and a chlorine content of about 57 to 59%. The above data, as graphically illustrated, show that a wax feed mixture comprising about 55 to 80%, preferably about 60 to soft wax and about 20 to 45%, preferably. about 25 to 40%, hydrocarbon oil must'be employed in order to obtain the desired melting point and chlorine content. The above data also shows that a hydrocarbon solvent may alsobe successfully employed in conjunction with the wax and thehydrocarbon oil prof vided that the amount of hydrocarbon oil employed does not constitute less than about 20% by weight of the wax feed mixture. The desiredchlorinated wax compositions preparedby the method outlined above have'a density ranging from about 1.290 to l.350.

It will be understood that the invention is not necessarily limited by the reactants and the operating conditions employed in the foregoing example. The reactants and operating conditions may be varied withinthelimits indicated in the general portions of the specification. I

1. A process for the preparation of a chlorinated wax composition having a melting point of about 40f .to 44 C. and a chlorinefcontent of about 56 to 60 wt. which comprises chlorinating a mixture comprising about 55 to Wt. of a soft paraifin wax having a molecular weight of about 280 to 400 and about 20 to 45 wt.% of a paraffinic hydrocarbon oil having a molecular weight of about 280 to 400 with chlorine. f

2. The process of claim 1 wherein said mixture also contains about5 to 25 wt. ofa hydrocarbon solvent comprising branched chain, saturated hydrocarbonsjhaving at least 11 carbon atomsper molecule. u

3. The process of claim2 wherein said hydrocarbon solvent has an average molecular weight of about 180 and a boiling pointof about 190 to240 C. j

4. The process of claim lwherein said parafiin wax has a meltingpoint of about 37 to 47 C..

, 5. The process of claim lwherein said hydrocarbon oil has a molecular Weightat least equal to the molecular weight of said soft parafiin wax.

6. A process for the preparation of 'a chlorinated wax composition having a melting point of about 41f to 43 C. and a chlorine content of about 57 to 59%, which comprises reacting amixture. of. about 60 to. 75 wtof a soft paraffin .wax having a melting point of about 37 to 47 C. and about25 to 40% of a paraffinic hydrocarbon oil having a molecular weight of about 280 to .400 with gaseous chlorine ata temperature of'about to C. and a pressure of about 10 to' 50 p.s.i.g., and reeOvering said chlorinated wax j composition.

7. The process of claim 6 wherein said mixture contains about 5 to 25 wt. of a hydrocarbon solvent comprising branched chain, saturated hydrocarbons having at least 11 carbon atoms per molecule and having a molecular weight of about 160 to 190. g

-8. The process of claim 6 wherein said mixture is chlorinated with gaseous chlorine in the presence of actinic light.

9. A light colored, stable chlorinated Wax composition having a melting point of about 40 to 44 C. and a chlorine content of about 56 to 60% prepared in accordance with the process of claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A PROCESS FOR THE PREPARATION OF A CHLORINATED WAX COMPOSITION HAVIN G A MELTING POINT IF ABOUT 40* TO 44* C. AND A CHLORINE CONTENT OF ABOUT 56 TO 60 WT. % WHICH COMPRISES CHLORINATING A MIXTURE COMPRISING ABOUT 55 TO 80 WT. % OF A SOFT PARAFFIN WAX HAVING A MOLECULAR WEIGHT OF ABOUT 280 TO 400 AND ABOUT 20 TO 45 WT % OF A PARAFFINIC HYDROCARBON OIL HAVING A MOLECULAR WEIGHT OF ABOUT 280 TO 400 WITH CHLORINE. 